Sebum-adsorbent powder and use thereof

ABSTRACT

There is provided a powder comprising a base substance usable as a powder for cosmetics, a hydroxyapatite and a zinc oxide, preferably a powder obtained on coating the surface of the substance with hydroxyapatite to form a hydroxyapatite coating layer on the surface of the base substance and fixing zinc oxide to the hydroxyapatite coating layer thereof, suitable for use in cosmetics.  
     The powder has a light reflection curve similar to that of the surface of the skin so that it exhibits good skin feeling and is superior in long wear effect for makeup and antibacterial effect.  
     This powder is also superior in adsorbing, solidifying or congealing the sebum components or body odor components, and is useful as effective components for a sebum-adsorbent agent, a body deodorant or the like in addition to the cosmetics.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a novel powder having aparticularly excellent sebum-adsorbent property, and to a cosmetics,sebum-adsorbent agent, a body deodorant and the like, each employing thenovel powder. More particularly, it relates to a powder comprising abase substance usable as a powder for cosmetics, a hydroxyapatite and azinc oxide, preferably to a powder obtained on coating the surface ofthe substance with hydroxyapatite and fixing zinc oxide to thehydroxyapatite coating layer thereof, and particularly suitable for usein cosmetics, such as a sebum-adsorbentagent, or a body deodorant, orthe like. It is possible to provide cosmetics, a sebum-adsorbent agent,a body deodorant and the like by the use of the powder in the presentinvention.

[0003] 2. Description of the Related Art

[0004] The sebum secreted from the skin affords an emollient effect tothe stratum corneum of the skin which keratinizes normally, preventsintrusion of toxic substance or bacteria from the outside, and controlsthe release of substances, such as water, out of the body. However,excess secretion of the sebum has a demerit that it may be a factor orso causing the makeup to come off which leads to some phenomena, forexample, a “shiny” or “drab” appearance of the skin, or a “unevenness”,“rumpling”, or “disappearance” of the makeup itself, and the like causedby chronological changes in the cosmetic film that is coated on theskin, that may be due to the formation of peroxides by the oxygencontained in atmospheric air. Similar to photo-degradation of fats andoils, such formation of peroxides, if intruded into the skin, operatesas irritants that may cause inflammation or a keratinization disorder,blemishes, or freckles on the skin. So, there is raised a demand fordeveloping a technology for effectively removing sebum, wherein it takesaccount of safeness of the skin so as not to impose an excessive burdenon the skin.

[0005] A variety of investigations have already been conducted from theviewpoint of improving long wear for makeup. For example, should highlymoisture-absorbent or oil-absorbent substances, such as porous silica,calcium carbonate, magnesium carbonate, and crystalline cellulose, bemixed into cosmetics, moisture and sebum components on the skin becomeadsorbed, which leads to a shortage of skin emollient components andcauses a dry skin feeling, and a tightness of skin or itchiness of skin.This phenomenon is most likely to occur with persons with dry skin andnormal skin, in particular with persons living in an environment and thelike (for example, persons working in an office) where perspiration(sweat) or sebum are not apt to be secreted. When used on oily skin,these substances have demerits, which are apt to present luster by theprogress of the wet phenomenon due to excess sebum or oily componentscontained in the cosmetics, thus giving rise to a “shiny” look in thefinished makeup.

[0006] Although cosmetics admixed with fluorine-processed powders havebeen proposed for improving the long wear for makeup, cosmetics makinguse of these powders, while not being wetted with sebum or perspiration,exhibits strong water- or oil-repellency thus causing the cosmetic filmto be “rumpled” due to slipping of the powder on the skin thus impairingthe makeup effect.

[0007] The cosmetics employing the powders treated with silicone arehigh in water repellency and also exhibit resistance againstperspiration and moisture. However, the silicone oil, and the siliconeoil or its derivative which is applied for surface treatment of thepowder are low in oil resistance, basically due to the basic structurewhich the silicone oil has. Consequently, in the case of a person withan oily skin, the makeup may come off from the entire face due to excesssecretion of sebum. On the other hand, in the case of a person withnormal skin, the makeup may come off at the T- or V-zone of the face, sothat it is difficult to prevent the makeup from coming off due tosecretion of sebum.

[0008] A film forming polymer material may be utilized for improvinglong wear for makeup. As representative of this type of substance, anacryl-silicone based graft polymer has been proposed. This is producedand obtained by radical polymerization of a dimethyl polysiloxanecomposite which has a radical polymerizability at one terminal end ofthe molecular chain with a radical polymerization monomer composedessentially of an acrylate or a methacrylate, and forms a cosmetic filmsuperior in water- and oil-repellency so that it is made practicable ina non-aqueous foundation. However, the cosmetics employing thesepolymers, from the viewpoint of enveloping the skin, leave many problemsof a physiological aspect in the skin when taking into consideration theeveryday biological activity on the surface of the skin. Moreover, inpowder products in which the skin-forming capability cannot be usedeffectively, long wear is difficult to be improved.

[0009] There are also proposed a zinc oxide coated substance in which abase substance is coated with an amorphous zinc oxide, and there arereported a powder exhibiting good spreadability without detracting fromthe fatty acid-solidifying capability and an external agent for skin,using this powder (see Japanese Patent Kokai Publication JP-A-9-227792).However, the amount of adsorption of an oleic acid, which the zinc oxidecoated substance exhibits, is approximately the same as that of thenormal porous silica and is not particularly excellent in adsorption ofthe free fatty acids. Moreover, the amount of adsorption of anartificial sebum, which this coated substance exhibits, is lesser thanthe porous silica beads, and furthermore this coated substance takesapproximately 30 minutes to solidify fatty acids, thus presentingdifficulties in coping with the oily skin or ultra-oily skin.

[0010] On the other hand, there are reports of a composite, which isinclusive of one or more oxides and/or their hydroxides in theinter-layer of the clay mineral or an inter-layer metal inclusivecomposite adsorbing selectively only free fatty acids (see JapanesePatent Kokai Publication JP-A-10-87420). This material uses awater-swollen type of clay mineral and is produced by the reaction inthe sol-state. As may be understood from the description of the Examplesthereof, the reaction takes place in the diluted solution. Therefore,this method is costly in production per batch and is economicallyunmeritorious. Moreover, since the reaction occurs in the sol-state, thewashing process is extremely time-consuming, when a regular filtering,washing, and drying process is used. The process is not only extremelytime-consuming, but also the obtained product aggregates strongly,thereby not obtaining the result that is expected. In addition, afreeze-drying process is essential so that production becomes veryexpensive as another weak point. Although AL pillars are formed in theinter-layer of the clay mineral, the variations of content ofintercalated oxide or hydroxide generates different states of pillarsbecause of differences between lots of the clay mineral, it is usuallydifficult to obtain products in the same stable quality.

[0011] There is also a demand for the development of a substance (agent)for absorbing, adsorbing, solidifying, or congealing the body odor(smell), which is a body deodorant, which may or may not be comprised incosmetics.

[0012] Under these above circumstances, there is a demand to develop asuitable skin-friendly powder, wherein the powder improves long wear formakeup, and can improve the demerits of the above prior substances, andcan adsorb sebum, and also has antibacterial effect and body deodoranteffect, in particular keep a cleanness and safeness of the skin by thecosmetics, by removing the free fatty acid (in particular theunsaturated fatty acid) and the secreted sebum.

SUMMARY OF THE INVENTION

[0013] Problem to be Solved by Invention

[0014] In view of the above, it is a problem to be solved by the presentinvention to provide a material suitable for use in cosmetics and thelike, wherein the material specifically adsorbs free fatty acids (inparticular unsaturated fatty acids), and also adsorbs, solidifies orcongeals the secreted sebum, does not obstruct the skin physiology bymaking a solid film form, and has a light reflection curve (reflectedlight curve) similar to that of the surface of skin, and has a good skinfeeling and is superior in long wear effect for makeup and antibacterialeffect, and also has a deodorant effect.

[0015] Means to Solve Problem

[0016] The present inventors have conducted perseverant researchestowards solving the above problem, and found that a powder comprising abase substance usable as a powder for cosmetics, a hydroxyapatite and azinc oxide, preferably a coated substance, obtained on coating ahydroxyapatite on the surface of the substance and fixing a zinc oxide,more preferably a low crystalline zinc oxide (and/or an amorphous zincoxide) to the coating layer, in particular the surface of that, of thehydroxyapatite, has such superior effects. It has also been found thatthe powder is superior in sebum-adsorbent property (in particular, thepowder has high adsorbent properties with respect to unsaturated fattyacid and sebum, and also the time for solidifying unsaturated fatty acidand sebum is short), and the powder has an antibacterial effect and aproperty for adsorbing body odor components. The above variety ofknowledge has led to the completion of the present invention.

[0017] That is, the present invention resides in a powder comprising abase substance usable as a powder for cosmetics, a hydroxyapatite and azinc oxide, preferably a powder comprising a base substance usable as apowder for cosmetics, a hydroxyapatite coated on the surface of saidsubstance and a zinc oxide fixed to the coating layer of saidhydroxyapatite. Preferably, that is a powder obtained on coating thesurface of the substance with hydroxyapatite to form a hydroxyapatitecoating layer on the surface of the base substance and fixing a zincoxide to the hydroxyapatite coating layer thereof. Moreover, the powderis suitable as a powder for cosmetics so that the powder can be appliedto the cosmetics admixed with the powder, or to other fields of use. Forexample, since the powder has the property of adsorbing sebum componentsand the effect of deodorizing the body odor, the powder can be used fora sebum-adsorbent agent, a body deodorant and the like, therefore, thepresent invention contains these embodiments.

[0018] Now a sebum-adsorbent agent means an adsorbent agent for sebum,or an agent for adsorbing sebum.

[0019] Meanwhile, it suffices if the powder of the present inventioncomprises the aforementioned three components (that is the substance,the hydroxyapatite and the zinc oxide), and the powder of the presentinvention may compose other components or other structures, as far asthe effect in the present invention is obtained or the object of thepresent invention is not obstructed. As a matter of course, thesecontents are contained in the powder of the present invention.

[0020] Meanwhile, as stated above, the sebum-adsorbent agent means asubstance used for adsorbing, solidifying, or congealing the sebum of ananimal, especially a human being. On the other hand, the body deodorantmeans a substance used for absorbing, solidifying, fixing, ordeodorizing at least one of the components of disagreeable odor emittedthrough the skin of an animal, especially the skin of a human being, orfrom the epidermic cell (for example, due to perspiration (sweat) oreffect of microorganisms and the like). In particular, the bodydeodorant may be used as the powder is mixed into the skin cosmetics orused as the powder mixed for deodorizing body odor separate fromcosmetics.

[0021] In the present invention, the body odor (smell) componentscompose of a broad sense of body odor components which is emitted fromthe animal, especially the human body (see Seiichi Izaki, What is Bodyodor—its Cause and Prevention, Fragrance Journal, 1990-7, p.22 to 26(1990); Yuuichi Yamamura, Body odor, ‘Modern Dermatology 2B’ Whole Bodyand Skin 2, edited by Yuuichi Yamamura, Jun Kukita, Eishun Sano, MakotoSeiji, published by NAKAYAMA SHOTEN, Tokyo, 1981, 163).

BRIEF DESCRIPTION OF THE DRAWINGS

[0022]FIG. 1 shows the measured results of the spectral reflectance asmeasured by a spectrophotometer for comparing the transparent feeling(transparency) in Example 2, where the sample:  denotes the skin(devoid of samples), ▪ denotes the sericite and ▴ denotes the inventivesubstance (Example 1).

[0023]FIG. 1(a) shows direct coating on the skin in an amount of 0.04g/58 cm² for the sample and FIG. 1(b) shows coating of the emulsion onthe underlying ground in an amount of 0.03 g/58 cm² for the sample.

[0024]FIG. 2 is a photo of the state of the skin (face) five hours aftercoating the face with the powder, as taken by a digital camera inExample 2 (comparison of the effect by use), under a light.

[0025]FIG. 2(a) shows the skin and right face and FIG. 2(b) shows theinventive substance (Example 1), left face.

[0026]FIG. 3 is a video microscope photo (magnification factor: ×200) inthe Example 2 (comparison of the effect by the use) as observed afterlapse of five hours after coating the face with the powder.

[0027]FIG. 3(a) shows the skin, right face and FIG. 3(b) shows theinventive substance (Example 1), left face.

[0028]FIG. 4 shows a photo taken by the digital camera in Example 6,with the photo taken under the light near the window for showing thestate of the skin (face) after lapse of five hours after coating theface with the powder foundation.

[0029]FIG. 4(a) shows the inventive substance (Example 3), right face,near the window;

[0030]FIG. 4(b) shows the product of the Comparative Example 1 forshowing the left face near the window;

[0031]FIG. 4(c) shows the use of the inventive substance (Example 3),right face, under the light;

[0032]FIG. 4(d) shows the use of a product of the Comparative Example 1,left face, under the light;

[0033]FIG. 4(e) shows a photo of FIGS. 4(c) and 4(d) simultaneously,with the left side face on the photo (right face) being coated with theinventive substance.

[0034]FIG. 5 is a video microscope picture in Example 6 (magnificationfactor, ×200) as observed five hours after coating the surface with thepowder.

[0035]FIG. 5(a) shows an inventive substance and

[0036]FIG. 5(b) shows a product of the Comparative Example 1.

PREFERRED EMBODIMENTS OF THE INVENTION

[0037] In the following, a preferred embodiment of the present inventionis explained in detail.

[0038] The powder of the present invention comprises a base substanceusable as a powder for cosmetics, a hydroxyapatite and a zinc oxide.Preferably, the powder comprising these components and which are in theform of a coated substance is cited. The following explanation iscentered about this coated substance. The powder of the presentinvention contains this coated substance only by way of an example, andtherefore is not limited thereto.

[0039] (Coated Substance (Composite Material) of the Present Invention)

[0040] The coated substance of the present invention has a basicstructure which is comprised of a base substance, a hydroxyapatitecoating layer on the surface of the base substance, and a zinc oxidefixed to the coating layer thereof, preferably to its surface. Morepreferably, low crystalline zinc oxide, amorphous zinc oxide or amixture thereof is used as a zinc oxide, and is fixed to thehydroxyapatite layer for forming the coated substance in the presentinvention highly useful as cosmetics. The substance can be employed fora powder usable as cosmetics, both inorganic and organic, and may beused in the form of variety of composite powders, such asinorganic-inorganic powders, organic-organic powders, inorganic-organicpowders, and the like. Among inorganic powders, there are clay minerals,metal oxides, metal hydroxides and composite materials comprising thesematerials, and the composite material(s) of one or more these inorganicmaterial(s) with one or more organic material(s). As the organicpowders, those usable for the substance of variety of cosmetics may beused. As a matter of course, natural products or synthetic clay mineralsmay be contained in the clay minerals. It is also possible to use acomposite material of the organic and inorganic powders, that is, theorganic-inorganic composite powders. In the case of using them in thecosmetics and the like, one or more of these powders may, of course, beused.

[0041] There is no particular limitation to the particle shape. Forexample, there may be a variety of shapes, such as lamellar shape,scale-like shape, plate-like shape, spherical shape, spindle shape,X-shape, starfish-like shape, ribbon-like shape, hemispherical shape,needle-like shape, bar-like shape and the like. The lamellar,scale-like, plate-like or bar-like shape is particularly preferred inthat it is ready to produce the same light reflection curve as thatobtained on the surface of skin.

[0042] The size of the particle in the powder used for the basesubstance, expressed as mean particle size, is preferably on the orderof 0.1 to 600 μm, more preferably on the order of 0.3 to 140 μm,moreover preferably on the order of 1 to 80 μm and most preferably onthe order of 2 to 50 μm.

[0043] In the present invention, the clay minerals used in the basesubstance, may be inclusive of synthetic products, and may be enumeratedby kaolins, such as kaolionite, dekkite, nacrite, halloysite,antigorite, chrysotile and the like, smectites, such as pyrophyllite,montmorillonite, nontronite, sabonite, hectorite, bentonite and thelike, illites, such as sericite, white mica, black mica, lithia mica,gold mica, synthetic mica, synthetic sericite and the like, silicates,such as calcium silicate, magnesium silicate, magnesium aluminumsilicate and the like, magnesium silicates, such as talc, serpentine andthe like, natural and synthetic zeolite, tourmaline and the like. Ifmetal oxides are used as the base substance, single component powder,such as silica, alumina, titanium oxide, cerium oxide and the like,bismuth oxychloride, barium sulfate and the like, may be used. Inparticular, plate-like shaped or scale-like (scalar) shaped products aredesirable. Moreover, the form of composite material may be used. Thecomposite oxides may be enumerated by multi-layered composite material,such as silica-titanium dioxide, silica-zinc oxide, silica-titaniumdioxide-silica, silica-cerium oxide-silica, silica-zinc oxide-silica andthe like, pearl pigments, such as titanium mica, colored titanium mica,titanium dioxide-barium sulfate, titanium dioxide-talc, zinc oxide-mica,zinc oxide-talc, bismuth oxychloride-mica and the like, the surface ofthese pearl pigments treated with aluminum hydroxide, aluminum oxide,magnesium hydroxide, magnesium oxide, silica, barium sulfate or thelike, and hard capsules, such as titanium dioxide encapsulating PMMA,zinc oxide encapsulating PMMA, cerium oxide encapsulating PMMA and thelike.

[0044] Among the organic powder used as a base substance, there are avariety of powders usable for cosmetics, such as nylon powders,polyethylene powders, polypropylene powders, polystyrene powders, vinylacetate powders, polymethacrylic acid ester powders, polyacrylonitrilepowders, cellulose powders and the like. The organic-inorganic compositepowders may be enumerated by polyethylene-zinc oxide,polyethylene-titanium dioxide, polyethylene-aluminum hydroxide,polyethylene-aluminum hydroxide-PMMA and the like. If theorganic-organic composite powders are used, nylon-cellulose may be used.

[0045] There is no particular limitation to the hydroxyapatite used inthe present invention. It is defined as calcium phosphate, with Ca/P=0.5to 2.0 (in molar ratio), having an apatite structure (see FragranceJournal, p144 to p148, 1999 January). Such calcium phosphate may be usedin the present invention.

[0046] The hydroxyapatite, that is coated on the surface of basesubstance, has the action of specifically adsorbing free fatty acids, inparticular unsaturated fatty acids. It may be presumed that this freefatty acid, somewhat exhibiting sebum-solidifying capability, operatesas a factor responsible for causing makeup to come off due to the actionof specifically lowering the melting point of the sebum. Thehydroxyapatite adsorbs free fatty acid secreted from the skin andprevents the makeup from coming off due to the lowering of the meltingpoint of the sebum. The hydroxyapatite also plays the role of keepingthe skin clean by the adsorptive action of peroxides generated due tooxidation of sebum secreted from the skin.

[0047] The hydroxyapatite coating that is coated on the surface of thebase substance increases its crystallinity by heat treatment, with thecrystallinity being higher, a higher heat treatment temperature beingnecessary. However, since the amount of the fatty acid adsorbed isinversely correlated with the heat treatment temperature, it is moredesirable not to apply heat treatment.

[0048] Although there is no limitation to the hydroxyapatite used in thepresent invention, as described above, Ca₅(PO₄)₃(OH), Ca₁₀(PO₄)₆(OH)₂,Ca₄(PO₄₎ ₂O, Ca₁₀(PO₄)₆F₂, Ca₃(PO₄)₂ and the like are cited preferablein view of safety.

[0049] The amount of hydroxyapatite used for coating is preferably onthe order of 2 to 50 wt %, more preferably on the order of 5 to 30 wt %and most preferably on the order of 10 to 20 wt % based on the weight oftotal composition of powder, in particular, the total weight of the basesubstance, the hydroxyapatite and zinc oxide. The coating amount lessthan 2% is insufficient to keep the skin clean due to the excessivelysmall amount of the adsorption. If the coating amount exceeds 50 wt %,the amount of adsorption cannot be expected to be increased inproportion to the amount used for coating. Moreover, the slipperiness(lubricant property) on the skin is undesirably lowered. Although thereis no limitation to the thickness of the coating layer, it is preferablyon the order of 0.05 to 4 μm and more preferably on the order of 0.1 to2 μm.

[0050] After coating the surface of the base substance with ahydroxyapatite, zinc oxide is fixed to the hydroxyapatite coating layer,for example, to its surface. As a zinc oxide for fixing, since zincoxide having high crystallinity is low in both free fatty acid-adsorbentproperties and sebum solidifying capability for solidifying the sebum,it is desirable to use low crystalline zinc oxide, amorphous zinc oxideor mixtures thereof. The particle size, expressed as mean particle size,is preferably on the order of 0.01 to 1 μm, more preferably on the orderof 0.03 to 0.5 μm, and most preferably on the order of 0.05 to 0.1 μm.

[0051] Meanwhile, “low crystalline”, in the low crystalline zinc oxide,means the state in which crystalline planes are not arrayed neatly innumerous random orientations of small-sized crystals. The X-raydiffraction peak width is determined by the variable orientations(arraying states) of individual micro-crystallites and the crystallinesize. In the case of the large crystalline size, light scattering issmall, whereas, in the case of the small crystalline size, the peakwidth is broad. The crystalline size may be obtained from the followingScherrer's equation:

[0052] (Scherrer's Equation)

L=(Kλ)/(β₀ cos θ_(B))

[0053] where

[0054] L=crystalline size in Å

[0055] K=constant (=1.0)

[0056] λ=wavelength of X-rays (=1.5406 Å

[0057] θ_(B)=Bragg's angle

[0058] β₀=(β_(E) ²−β_(I) ²)^(½)

[0059] β_(E)=apparent half value width (measured value)

[0060] β_(I)=constant of a mechanical device (=1.75×10⁻³ rad.)

[0061] Although the above equation is lowered in reliability when thenumerical value exceeds 1000 Å, it may be seen that the crystalline sizeof the low crystalline zinc oxide is evidently small in crystalline sizeas compared to that of the crystalline zinc oxide.

[0062] The result of calculating the crystalline size L of zinc oxide isas follows: HALF samples H K L 2THETA/DEG. WIDTH/DEG. L (Å) crystalline1 0 0 10.83 0.12 1562.5 zinc oxide 0 0 2 25.86 0.13 1091.1 low 1 0 010.79 0.46  196.3 crystalline 0 0 2 25.84 0.20  541.4 zinc oxide

[0063] For analysis, the (100) plane and the (002) plane of zinc oxideare used. The crystalline size represents the size in a directionperpendicular to these planes. In the low crystalline zinc oxide, thecrystalline size is larger in the (002) direction than in the (100)direction. In the crystalline zinc oxide, this relationship is reversed,such that growth occurs significantly in the (100) direction.

[0064] If the crystalline zinc oxide and the low crystalline zinc oxideare compared to each other, it may be seen that the crystalline zincoxide has a value exceeding 1000 Å in crystalline size, whereas the lowcrystalline zinc oxide obviously has a crystalline size not larger than1000 Å, thus being small in crystalline size.

[0065] As the low crystalline zinc oxide used in the present invention,the crystalline size of zinc oxide, expressed aforementioned crystallinesize, preferably 100 nm (1000 Å) at most (at the longest), morepreferably 2 to 100 nm (20 to 1000 Å) and most preferably 3 to 100 nm(30 to 1000 Å)

[0066] The “amorphous”, in the amorphous zinc oxide, is defined as beingin the solid state in which the crystal lattice (periodic array ofatoms) is hardly noticed or as being a solid which fails to give anX-ray diffraction image even if there exists certain periodic array ofatoms

[0067] Although the sebum composition differs with the sex and with age,with the result done by the researches of SHISEIDO KK, in the case of afemale, the sebum comprise free fatty acid on the order of 7 to 13%,squalene on the order of 11 to 17%, wax on the order of 14 to 17%,triglyceride on the order of 47 to 55%, diglyceride on the order of 3 to5%, monoglyceride on the order of 0.7 to 1.2%, stearin esters on theorder of 1.4 to 1.5% and free stearins on the order of 1.4 to 1.5%.Therefore, if approximately 7 to 13% of free fatty acids in the sebumcomposition only is adsorbed, many other sebum components remains on theskin, such that the prevention of the makeup from coming off is doneinsufficiently, and hence it is necessary to adsorb, solidify or congealother secreted sebum components to prevent the sebum from beingfluidized.

[0068] The powder of the present invention has particularly superiorfeatures in specifically adsorbing free fatty acid in the sebumcomposition and also prevents the melting point of the skin from beinglowered, and in exhibiting higher sebum-solidifying capability withhigher capability of adsorbing fatty acid (fatty acid-adsorbingcapability), through the interaction between the action of adsorbing theother sebum components, such as diglyceride or triglyceride and ester,and the sebum-solidifying capability. Moreover, the powder of thepresent invention can keep the skin clean because it has properties offorming a strong cosmetic film that prevents the makeup from coming offand adsorbing the peroxides generated by oxidation of sebum, and havingantibacterial activities. The cosmetic film obtained according to thepresent invention is superior in transparency, exhibits the same patternas that of the skin's spectroscopic curve, and prohibitsnon-transparency or the whitish powder floating on the makeup finish.Moreover, its adherency to the skin and skin feeling are given in so faras the cosmetic effect is concerned, while the aesthetic feel is alsoequivalent to that of the scale-like powders routinely used in thecosmetics.

[0069] The amount of zinc oxide used in the powder of the presentinvention is preferably on the order of (approximately) 2 to 8 wt %,more preferably on the order of (approximately) 3 to 7 wt % and mostpreferably on the order of (approximately) 4 to 6 wt % based on thetotal composition (weight) of the powder, in particular the total weightof the base substance, the hydroxyapatite and the zinc oxide involved.The amount of zinc oxide less than 2 wt % or exceeding 8 wt % are bothundesirable in that the sebum-solidifying capability is markedly loweredin the former case, whilst the sebum-solidifying capability tends to belowered due to interaction in the latter case.

[0070] The coated powders of the present invention can be producedwithout particular difficulties by, for example, the following method:

[0071] A liquid comprising a base substance dispersed therein is addedto calcium acetate and is heated to 85° C. and admixed with a mixedsolution of sodium hydroxide and disodium hydrogenphosphate (Na₂HPO₄).The pH value then is adjusted to approximately 9 to 10. The resultantproduct then is added to a sodium hydroxide solution and the pH value isadjusted to approximately 11 to 12. The resultant product is kept atapproximately 85° C. and cured. After the end of curing, the solution iscooled and set at a temperature of approximately 60° C. When thetemperature is at 60° C., the reaction mixture is adjusted to the pHvalue of approximately 12 by adding a 5N sodium hydroxide solutionthereto. As the pH value is adjusted to and kept at approximately 12, a1M zinc chloride solution and a 5N sodium hydroxide solution are drippedinto the reaction mixture simultaneously. After that, the reactionmixture is cooled, filtered and washed with water repeatedly. Thereaction product is dried at 120° C. for 16 hours or so and pulverizedto obtain a coated powder of the present invention. The coated substanceof the present invention, obtained as described above, specificallyadsorbs the free fatty acids while simultaneously adsorbing andsolidifying other sebum components, while maintaining its aestheticfeel, and is superior in the long wear effect for makeup, skincleanliness (cleanness of the skin) and skin feeling, and inantibacterial properties.

[0072] Thus, the coated substance of the present invention is suited asa starting material for preparations of cosmetics and drugs. Inparticular, it is useful as a starting material for cosmetics since itis excellent in long wear for makeup and in antibacterial properties,while maintaining skin cleanliness and skin feeling. Moreover, it may beused as a sebum-adsorbent agent or as a body deodorant.

[0073] (Cosmetics)

[0074] The cosmetics of the present invention have features in that itcomprises the coated substance (powder) of the present invention asdescribed above. The cosmetics of the present invention can be appliedto any agent form known for ordinary cosmetics, in particular it is notlimited. These cosmetics may be applied to, for example, basiccosmetics, such as cream, emulsion, lotion, sun-cam lotion and the like,point makeup agents, such as under-makeup, foundation, eye-shadow, lipcream, rouge brusher, lip gloss, lip color and the like, powderproducts, such as talcum powder, caramine lotion, baby powder, bodypowder, deodorant powder, fragrance powder, face powder and the like,and hair treatment products. The cosmetics of the present invention canalso be applied to wet tissues, oil removing sheets or makeup removingagents and the like. In particular, the cosmetics of the presentinvention can be more desirably enumerated by makeup cosmetics, basiccosmetics and sweat controlling cosmetics (especially deodorantcosmetics and the like).

[0075] The reason is that the coated substance of the present inventionexhibits a deodorant effect and antibacterial properties and, when thecoated substance of the present invention is used as cosmetics, itexhibits a high adsorptive power for free fatty acids and sebumcomponents, while being superior in long wear for makeup and skinfeeling.

[0076] When the coated powders of the present invention is composed incosmetics, there is no particular limitation to the amount of mixing inthe cosmetics since it may be suitably selected depending on the type ofthe cosmetics. In general, preferably on the order of 0.01 to 50 wt %,more preferably on the order of 0.05 to 30 wt % and most preferably onthe order of 0.1 to 20 wt % may be mixed in the entire cosmetics.

[0077] In addition to the coated substance of the present invention,those components used in routine cosmetics may be used. These componentsmay be enumerated by hydrocarbons, such as vaseline, micro-crystallinewax, ceresin, squalane, fluid paraffin and the like, higher alcohol,such as cetanol, stearyl alcohol, olein alcohol and the like, fattyacids, such as stearic acid, palmitic acid, behenic acid and the like,triglycerides, such as beef tallow, olive oil and the like, esters suchas myristic acid octyl dodecyl, dimethyl octanoic acid hexyldecyl,myristic acid isopropyl and the like, polyhydric alcohols, such asglycerine, 1,3-butylene glycol and the like, nonionic surfactants,anionic surfactants, amphoteric surfactants, cationic surfactants,ethanol, thickeners, such as carboxy vinyl polymer, carboxy methylcellulose sodium and the like, antiseptics, UV light absorbents,antioxidants, dyes and powders.

[0078] (Sebum-adsorbent Agent)

[0079] The present invention contains a sebum-adsorbent agent. Inparticular, the present invention may be applied with the intention orthe power of adsorbing, solidifying or congealing the sebum componentsof a human being. Therefore, the sebum-adsorbent agent also encompassesthe aforementioned cosmetics. The product of the present invention mayalso be used as a sweat controlling agent in addition to the cosmetics.The content of the powder to be mixed to the sebum-adsorbent agent canbe selected suitably. If the product of present invention is used forobjects other than cosmetics, the amount of mixing used in the cosmeticscan be used as reference values.

[0080] (Body Deodorant)

[0081] Usually, the body deodorant can be mixed into cosmetics foradsorbing, solidifying or congealing the body odor (smell) and the like,that is undesirable odor components emitted by perspiration ormicroorganisms through the skin of animals, in particular the skin ofhuman being, and can decrease the odor. According to the presentinvention, a body deodorant is a substance (agent) used for adsorbing orsolidifying at least one odor component emitted in particular from thehuman body through the skin, and the like, for reducing the odor(smell). The use thereof to the cosmetics is as described above. It canbe affected by using the formulation customarily used or known asdeodorant or antibromic agent (see Yoshihiro Ohhata, Tendency and Taskof Recent Body Deodorant Products, Fragrance Journal, 1990-7, p-61 to69, 1990). The amount of mixing of the powder of the present inventioncan be selected suitably depending on the species of agent form and thelike. Usually, the amount of mixing, which is shown in theabove-described cosmetics is referred.

[0082] This application is based on the Japanese Patent Application Ser.No.2000-204587, field on Jul. 6, 2000, which is incorporated herein byreference in its entirety.

EXAMPLES

[0083] The present invention is explained in detail by referring to thefollowing Examples and Comparative Examples.

Example 1

[0084] Preparation of Powder

[0085] 95 g of sericite (mean particle size: 8 μm, plate crystal) weredispersed in 1000 ml of purified water in the reaction vessel. To theresultant liquid dispersion 32.4 g of calcium acetate were added and theresultant mixture was heated to 85° C. When the temperature is 85° C., asolution obtained on dissolving 6.0 g of sodium hydroxide and 15.9 g ofdisodium hydrogenphosphate in 350 ml of purified water was added to theheated mixture to adjust the pH value of the solution to 9.4. A solutionobtained on dissolving 1.35 g of sodium hydroxide in 200 ml of purifiedwater was then added to the mixture to adjust the pH value thereof to11.4. The reaction mixture was subjected to reaction and curing for onehour. When the curing was finished, the reaction mixture was cooled to60° C., and 75 ml of 1M zinc chloride was added drop wise thereto, asthe pH value was kept at 12, using a 1M zinc chloride solution and 5Nsodium hydroxide solution. At the end of the dripping, the reactionmixture was cooled, filtered and washed with water repeatedly. Thereaction product was dried at 120° C. for 16 hours and pulverized toobtain a coated product (powder) of the present invention.

Example 2

[0086] Various Evaluation Tests for Powder

[0087] (Test Method)

[0088] A. Amounts of Adsorption of Various Fats and Oils and ArtificialSebum

[0089] 5.0 g of a sample was weighed out precisely in a 300 ml beakerand, as an example of fats and oils, 50.0 g of the artificial sebum wereweighed out precisely. In this time, if the artificial sebum is in thesemi-solid state, it is heated to hive a complete solution, and thenweighed out precisely. Each weighed sample was agitated vigorously for30 minutes by a magnetic stirrer and placed stationary for 18 hours in aconstant temperature chamber at 32° C. The samples were taken out fromthe constant temperature chamber and added to with 100 ml of petroleumether. After the resultant product was agitated for 30 minutes, theproduct was filtered. This operation was repeated thrice and theresultant product was dried at 80° C. The resultant sample was weighedout precisely and was held at 500° C. for four hours and fired and theamount of adsorption was obtained from the decreased amount of thesample.

[0090] The amount of adsorption of the artificial sebum in a mixedsystem of the artificial sebum and the pseudo-perspiration compositionwas measured in the same way as the above description by using 5.0 g ofthe sample to the equation:

Perspiration composition (g)/Artificial sebum (g)=20/80 to 80/20.

[0091] B. Fatty Acid-solidifying Capability (Solidification StartingTime)

[0092] 3.6 g of oleic acid was precisely weighed out in a 50 ml beakerinto which 1.0 g of the sample was charged and vigorously stirred andhomogeneously mixed for ten minutes with a magnetic stirrer. The liquidmixture was set stationary and the beaker charged with the sample wastilted (inclined) and fluidized. When the beaker was returned to theoriginal stationary set state, the time during which the deformed shapeon tilting was maintained was used as the solidifying capability(solidification starting time).

[0093] C. Transparency by Spectroscopic Photometer (Skin Feeling)

[0094] An area 58 cm² was fixed, using the arm of a forearm flexedportion and 0.04 g of the sample was uniformly coated using a urethanepuff. The reflectance of the spectroscopic reflected light was measured.The underlying ground was coated with an emulsion and 0.03 g/58 cm² ofthe sample was coated on the same site to effect similar measurement(using a spectroscopic photometer SZ-Σ90 manufactured by NIPPON DENSHIKK).

[0095] D. Coefficient of Dynamic Friction (Dynamic FrictionalCoefficient)

[0096] Using a friction sensory tester KES-SE manufactured by KATOTECKK., the pressure sensitive portion and the powder surface werereciprocated three times, the coefficient of dynamic friction (thedynamic frictional coefficient) was measured.

[0097] E. Amount of Absorption of Oil

[0098] 5.0 g of the sample was taken on a glass plate and squalane as acomponent similar to sebum was applied drop wise thereto. The reactionmass was kneaded homogeneously with a spatula until the sample wascollected as a sole mass. At this point, as an end point, the amount ofsqualane dripped until this time was used as the amount of absorption ofoil of the sample (ml/100 g)

[0099] (Evaluation Test as to a Variety of Powders)

[0100] (1) Amount of absorption of oil, specific surface, amount ofadsorption of oleic acid, amount of adsorption of artificial sebum andfatty acid-solidifying (oleic acid solidification starting time).

[0101] The measured results are shown in the following Table 1. TABLE 1amount amount of of amount of absorp- adsorp- adsorp- time tion tion oftion of of of oil specific oleic artificial solid- ml/100 surface acidsebum ifica- samples g m/g mg/g mg/g tion sericite 87 7.8 7.3 xcrystalline 92 9.3 17.4 89 min zinc oxide low 241 61.9 418.0 33 seccrystalline zinc oxide hydroxy- 223 63.1 59.1 x apatite smectite 62228.3 137.9 x hectorite 49 340.3 175.0 x magnesium 420 357.7 292.0 xaluminum silicate porous 147 305.4 71.5 65.3 x spherical silica titanium48 12.0 0.7 x dioxide (rutile type) Japanese 95 8.7 73.3 40.0 32 minPatent Kokai Publication JP-A-9- 227792 inventive 130 19.9 229.0 204.6 8 min substance (Example 1)

[0102] If evaluation is made from the results of the amount ofabsorption of oil, specific surface, amount of adsorption of oleic acid,amount of adsorption of artificial sebum and fatty acid-solidifyingpower (time of solidification), the inventive substance (powder of theExample 1) has an amount of oil absorption (amount of absorption of oil)which is slightly higher than the amount of oil absorption of 90 to 120of the powder mixed as a main filler, a high amount of oleic acidadsorption (amount of adsorption of oleic acid), a high amount of oleicacid adsorption per unit specific surface and a high amount ofartificial sebum adsorption (amount of adsorption of artificial sebum)and a shorter oleic acid solidification starting time. Moreover, the ininventive substance is evidently superior to the zinc oxide coatedsubstance as a prior product (see Japanese Patent Kokai PublicationJP-A-9-227792) in the amount of absorption of oleic acid, the amount ofadsorption of sebum, the amount of adsorption of artificial sebum andthe solidification starting time.

[0103] (2) Amount of Adsorption of each Fats and Oils for the InventiveSubstance

[0104] The amount of each fats and oils adsorbed for the inventivesubstance was measured and the results are shown in the following Table2: TABLE 2 amount of adsorption fats and oils mg/g glycerine tri-2-ethyl18.4 hexanoate glyceryl dioleate 35.2 O.D.O. manufactured 24.4 byNISSHIN SEIYU KK octyl dodecyl oleate 20.9 methyl polysiloxane* 11.8isostearic acid 42.5 oleic acid 229.0 squalene 24.0

[0105] It may be seen from the measured results of the amount ofadsorption, that the inventive substance specifically adsorbs free fattyacids and in particular unsaturated fatty acid selectively, and that theinventive substance also exhibits an adsorptive power for saturatedfatty acids, triglycerides, diglycerides, esters and the like, thusbeing superior in the sebum adsorptive power.

[0106] (3) Amount of the Adsorption in the Mixed System of theArtificial Sebum (Manufactured by MIYOSHI KASEI KK) and thePseudo-perspiration (Sweat) Components for the Inventive Substance

[0107] The amount of adsorption of the artificial sebum, with respect tothe inventive substance (Example 1), was measured and a comparison wasmade based on the compositions. The results are shown in the followingTable 3: TABLE 3 pseudo- amount of perspiration artificial adsorption ofcomponents sebum artificial sebum g g mg/g 20 80 220.9 50 50 236.6 80 20241.1

[0108] Meanwhile, the test was conducted using 5.0 g of the sample.

[0109] (Composition of Pseudo-perspiration (Sweat) Components)

[0110] The pseudo-perspiration (sweat) components are in the compositionof: 98% of purified water, 0.5% of urea, 1.0% of sodium chloride and0.5% of glucose.

[0111] On the human skin, there are 100 to 150 perspiration (sweat)glands on an average per 1 cm². The perspiration (sweat) glands areroughly divided into eccrinic (eccrine) glands and apocrine glands. Ifthe perspiration from both of these glands is summed together, thesecreted amount (the amount of secretion) in the still state is 300 to500 cc per day and in an ordinary life environment is 2000 to 3000 ccper day. The face subjected to makeup is not an exception. What iscrucial in actuality is not the amount of the moisture dissipated andevaporated from the skin surface (the surface of skin) but thecorrelation between the perspiration (sweat) retained on the skin,secreted sebum and the makeup film. It is seen that, in the perspirationto sebum mixed system, the amount of adsorption of the artificial sebum(the adsorbed amount of the artificial sebum) is not lowered even if alarge amount of perspiration is secreted, but rather the adsorbed amount(the amount of adsorption) is increased, there being no obstruction ofthe adsorbed amount of the sebum (the amount of sebum adsorption) by theperspiration. It is also seen from the experiments on the secretedamount equal to 20 times as much as the sample that a uniform solid filmfree of fluidity, such as w/o, is produced in the range of the sebum toperspiration ratio of 8/2 to 5/5. In actuality, the pigments and powdersin the makeup cosmetics are captured in the solid film. In addition, thefree fatty acid in the sebum is presumably adsorbed in the inventivesubstance to suppress the lowering of the sebum to form a solid filmwith more solid content and a stronger cosmetic film to assure superiorlong wear effect for makeup.

[0112] (4) Comparison of Transparent Feeling (Transparency)

[0113] The spectral (spectroscopic) reflectance was measured by aspectroscopic photometer for determination of transparency. Themeasurement method is as described above. As equipment for measurement,a spectroscopic photometer SZ-Σ90 manufactured by NIPPON DENSHI KK wasused.

[0114] For comparison, sericite superior in transparency and aestheticfeel, and hence used extensively as a powder product was used as acontrol substance. The results are shown in FIGS. 1(a) and 1(b). Whenthe powder is directly applied to the skin (see FIG. 1(a)), a patternhighly similar to the spectroscopic (spectral) reflected (reflection)curve of the skin is exhibited in case of coating of the inventivesubstance (Example 1), whilst the reflectance is slightly higher in thewavelength range of 400 to 600 nm, with the transparency (transparentfeeling) being high and thereby creating an effect of making the skinlook brighter. Conversely, in coating sericite, the reflectance isgenerally high such that relatively whiteness is felt strongly, with thespectroscopic curve slightly differing from the spectroscopic curve ofthe skin. If the emulsion is coated on the underlying ground (see FIG.1(b) approximately the same spectroscopic curve is displayed with thesame reflectance as the skin, with the spectroscopic reflection beingthe same as that of the surface of skin to demonstrate the effect of theappearance of the skin itself, that is, the minute texture of the skin.

[0115] (5) Measurement of the Coefficient of Dynamic Friction

[0116] (Dynamic Frictional Coefficient)

[0117] The measurement method is the same as described above. As theequipment for measurement, a friction sensory tester KES-SE manufacturedby KATOTEC KK was used. As samples, the inventive substance (Example 1),sericite used as a base substance in the Example 1, mica havingsubstantially the same chemical composition as sericite in being thesame material type as the sericite, and two sorts of composite materialsin consideration that the inventive substance is the composite material,were selected for measurement.

[0118] The results are shown in the following Table 4. The inventivesubstance is slightly higher than sericite in the coefficient of dynamicfriction (dynamic frictional coefficient), with the difference beingextremely small, with the slipperiness being substantially the same.Conversely, the mica or the composite powders are higher than theinventive substance (Example 1) in the coefficient of dynamic frictionand are clearly worse in the slipperiness. In the coefficient of dynamicfriction (the dynamic frictional coefficient), the inventive substanceis approximately equivalent to sericite which is used in large amount asa general filler and which is superior in aesthetic feel, however, inspite of composite material, in distinction from the functionalcomposite material in extensive use in general, it may be estimatedenough that the aesthetic feel is not lost if the inventive substance ismixed in large amount into the cosmetics. TABLE 4 samples MIU × 10⁻¹inventive substance 2.23 sericite 2.18 mica 2.85 Composite powder (A)*¹3.30 Composite powder (B)*² 2.96

[0119] (6) Antibacterial Power Test and Test Result

[0120] (Test Schematics)

[0121] To a liquid culture medium, admixed with the specimen having anarbitrary concentration, a bacterial solution of Escherichia coli orStaphylococcus aureus was added. After the liquid culture medium wascultivated under a shaking condition at 35° C. for 18 to 24 hours, thegrowth or existence of bacteria was checked. The results are shown inTable 5.

[0122] 1. Test Method

[0123] 1) Test Bacteria

[0124]Escherichia coli IFO (Escherichia coli)

[0125]Staphylococcus aureus IFO 13276 (Staphylococcus aureus)

[0126] 2) Culture Medium for Test

[0127] MHB culture medium: Mueller Hinton Broth [DIFCO LABORATORIESINCORPORATED]

[0128] SCDLPA culture medium: SCDLP agar culture medium manufactured byNIPPON SEIYAKU KK]

[0129] 3) Preparation of Bacterial Solution for Inoculation

[0130] Test bacteria cultivated over plural generations were inoculatedon a MHB culture medium. After cultivation at 35° C. for 18 to 20 hours,the culture was diluted on the MHB culture medium so that the number ofbacteria will be approximately 10⁴/ml for use as a bacterial solutionfor inoculation.

[0131] 4) Preparation of Culture Medium for Measuring the Sensitivity

[0132] After the specimen was sterilized under dry heating (at 180° C.for 60 minutes), a 10.5 and a 4 W/V % of liquid suspensions of thespecimen were prepared using the MHB culture medium. Moreover, as the 4W/V % of liquid suspension was agitated sufficiently, the liquidsuspension was sequentially diluted on the MHB culture medium by afactor of two to prepare a dual stage diluted liquid of the specimen. 10ml each of the prepared liquid suspension and each diluted solution werecharged into plural L-shaped test tubes for using as a sensitivitymeasuring culture medium.

[0133] 5) Cultivation

[0134] 0.1 ml of a bacterial solution for inoculation was inoculated onsensitivity measurement culture medium and cultivated under a shakingcondition at 35° C. for 18 to 24 hours.

[0135] 6) Judgment

[0136] With respect to the culture medium for measuring the sensitivityof the present test, the growth or existence of bacteria by observationwas not possible to judge due to turbidity caused by addition of thespecimen. So, a viable count (the number of live bacteria) of theculture medium for measuring the sensitivity was measured after the endof cultivation (SCDLPA culture medium, 35° C. for two days) and thecases of the number of bacteria per 1 ml of not larger than 106 andlarger than 106 were judged to be the case of “growth of bacteria notbeing recognized” and the case of “growth of bacteria being recognized”,respectively. TABLE 5 Growth or existence of Test Bacteria in CultureMedium Added to Specimen* test concentration of specimens added (%)bacteria 0.125 0.25 0.5 1 2 4 5 10 Escherichia + + + − − − − − coliStaphylococcus + − − − − − − − aureus

[0137] (7) Comparison of Cosmetic Effect with Use

[0138] The result of the comparison of the skin coated with powder(inventive substance; Example 1) and the uncoated skin was evaluatedafter 5 hours by photographing and video microscope. The results ofevaluation are shown in FIGS. 2 and 3. The result of comparison byphotographing indicated that the face with a glare clearly in case of anuncoated face (see FIG. 2(a)), whereas such “shine” was reducedappreciably in case of coating of the inventive substance (see FIG.2(b)). On the other hand, the result (see FIG. 3) of comparison by videomicroscope indicated that the sebum was seen to have been collected atthe near point from the skin wrinkle grooves and glared in case of anuncoated face (see FIG. 3(a)), whereas the powder was seen to haveadhered evenly to the skin surface (the surface of skin) while nodegradation of the makeup from coming off was observed, in case ofcoating of the inventive substance (see FIG. 3(b)), thus indicating thatthe inventive substance demonstrates a superior cosmetic effect.

[0139] (8) Deodorant Effect Test and Test Result

[0140] (Samples)

[0141] As a specimen, powder prepared in Example 1 was used. Forcomparison, sericite (mean particle size: 8 μm; plate-like shape) wasused as control specimen.

[0142] (Deodorant Components)

[0143] The deodorant effect was tested for ammonia, acetic acid andmercaptan.

[0144] (Test schematics)

[0145] Each 1 g of a specimen and a control specimen were charged eachinto an odor bag into which 3 liters of air were charged and weresealed, and subsequently ammonia was added to prepare a gasconcentration of approximately 500 ppm. The gas concentration in the bagwas measured chronologically. Similar tests were conducted for aceticacid (approximately 50 ppm) and methyl mercaptan (approximately 50 ppm).

[0146] 1. Reagents and Tools

[0147] An odor bag manufactured by MIYAKO VINYL KAKOSHO LTD., ammoniawater (28%, special grade) manufactured by KOMUNE KAGAKU YAKUHIN KK,acetic acid (special grade) manufactured by KOMUNE KAGAKU YAKUHIN KK, agas evolved on adding dilute sulfuric acid to a methyl mercaptan sodiumsolution (15%), as methyl mercaptan and a gas detecting tubemanufactured by GAS TEC KK., were used.

[0148] 2. Operations

[0149] As samples, each 1 g of a specimen and a control specimen waseach charged into an odor bag (25 cm×40 cm) and the bag was heat-sealed.Subsequently, 3 liters of air were charged and were sealed into the bagand ammonia was added to prepare a gas concentration of approximately500 ppm. The samples, so prepared, were allowed to stand under roomtemperature and the gas concentration in each bag was measured by a gasdetecting tube in 0.5, 1, 3, 6 and 24 hours thereafter. As for aceticacid (approximately 50 ppm) and methyl mercaptan (approximately 50 ppm),similar tests were conducted with the measurement time of 2, 5 and 10minutes and with the measurement time of 10 minutes, respectively.Similar tests were also conducted without charging samples (no sample)by way of a void test.

[0150] (Test Result)

[0151] Tables 6 to 8 indicate test results on ammonia, acetic acid andmethyl mercaptan. TABLE 6 ammonia (unit: ppm) time elapsed (hours)samples 0.5 1 3 6 24 Example 1 160 160 130 110  80 Control 350 350 310290 180 Void 490 490 450 410 300

[0152] By way of the initial condition, the gas concentration wasprepared to approximately 500 ppm. TABLE 7 acetic acid (unit: ppm) timeelapsed (minutes) samples 2 5 10 Example 1 2 1 <1 Control 7 7 7 Void 5050 50

[0153] By way of the initial condition, the gas concentration wasprepared to approximately 50 ppm. TABLE 8 methyl mercaptan (unit: ppm)time elapsed (minutes) samples 10 Example 1 <10 Control 50 Void 50

[0154] By way of the initial condition, the gas concentration wasprepared to approximately 50 ppm.

[0155] From the results of the above tables 6 to 8, it may be seen thatthe inventive powder exhibits superior deodorant effects, in particular,that the inventive powder exhibits superior effects of deodorizing theemission of disagreeable odor, that is, a body odor (unusual body odorcomponents).

Example 3

[0156] Preparation of Powder Foundation

[0157] A powder foundation having the following composition wasprepared. Foundation Composition parts by components weight powders talctreated with silicone 8.38 sericite treated with silicone 21.24inventive substance (Example 1) 19.76 mica treated with silicone 7.00titanium dioxide treated with 12.00 silicone polyethylene powder 13.00methyl paraben 0.20 red iron oxide treated with 1.37 silicone yellowiron oxide treated with 3.29 silicone ultramarine blue treated with 0.32silicone iron black treated with 0.12 silicone oily glycerinetri-2-ethyl 3.00 agents hexanoate squalane 1.50 nonionic surfactant 0.30d-δ-tocopherol 0.02 methyl polysiloxane* 8.50

[0158] (Preparation Method)

[0159] The powder components were mixed for three minutes in a Henschelmixer and taken out. Subsequently, the mixture so taken out waspulverized using a screen with a diameter of 0.5 m/mp. This resultantpulverized mixture was charged into a Henschel mixer and added to withoily agents for coating. Using a Herringbone screen of 1.0 m/m, themixture was powdered by a pulverizer. After this pulverized mixture wascharged into a metal mold, it was pressure molded to obtain a powderfoundation.

Example 4

[0160] Amount of Adsorption of Oleic Acid and Amount of Adsorption ofArtificial Sebum

[0161] In the powder foundation, obtained in aforementioned Example 3,the amount of adsorption of oleic acid and the amount of adsorption ofartificial sebum were measured and compared to conventional products(prior substances). The results are shown in Table 9. TABLE 9 amount ofadsorption amount of of oleic adsorption of acid artificial sebumsamples (mg/g) (mg/g) inventive substance 127.5 126.3 (Example 3)Conventional product 77.2 54.5 (prior substance) (A) Conventionalproduct 289.7 70.4 (prior substance) (B) Conventional product 66.9 63.9(prior substance) (C) Conventional product 86.6 96.6 (prior substance)(D)

[0162] The inventive substance (Example 3) only exhibited high values ofthe amounts of adsorption of both oleic acid and the artificial sebum.The conventional product (prior substance) (B) and the inventivesubstance exhibited specifically a selective adsorption for free fattyacids. It may also be seen that the inventive substance exhibitedadsorbent effects for a mixed system of a variety of substances, such atriglycerides, diglycerides, free fatty acids, squalene and the like,such as artificial sebum, which are apparently superior to those of theconventional products.

Example 5

[0163] Evaluation of Usability

[0164] The powder foundation obtained in Example 3 was evaluated. As acontrol substance (Comparative Example 1), a powder foundation preparedin accordance with Example 3 except substituting a sericite treated withsilicone for all of the powder of Example 1 was used. For evaluationmethod, six expert peoples in a panel actually used the powderfoundation and, after use, five-stage evaluation was conducted as to thefollowing evaluation items in accordance with the following standard:(Evaluation standard) 1 2 3 4 5 long wear bad

good transparency no

yes extension on skin bad

good makeup finish not beautiful

beautiful affixture no

yes adhesion bad

good

[0165] (Result of Evaluation) items of Comparative evaluation Example 3Example 1 long wear 4.9 1.1 transparency 4.2 2.2 extension on skin 3.63.6 makeup finish 4.8 2.7 affixture 4.6 2.6 adhesion 4.5 3.8

Example 6

[0166] Evaluation of Long Wear for Makeup by Photographing and the Like

[0167] The long wear for makeup was evaluated on the powder foundationof the inventive substance (Example 3) by photographing and by the useof a video microscope.

[0168] (1) The powder foundation was coated on a face, and theappearance of long wear for makeup after lapse of five hours wasphotographed using a digital camera. FIG. 4 shows the result ofcomparison to the powder foundation of the Comparative Example 1(without using the inventive powder) prepared in Example 5.

[0169] It is seen from these results that the makeup by the product ofComparative Example 1 (FIG. 4(b) and FIG. 4(c)) indicated “shine” due tosebum not only at a site near the window but also under the light,whereas the inventive substance looks natural thus understanding to besuperior in long wear for makeup.

[0170] (2) The powder foundation was coated on the face and theappearance of the long wear for makeup after lapse of five hours wasphotographed with a video microscope with a magnification factor of×200. FIG. 5 shows the result of comparison with the powder foundationof the aforementioned Comparative Example 1.

[0171] These results indicated to the superior long wear of theinventive substance for makeup. That is, it may be seen that, withrespect to the makeup by the inventive substance, the powder are adheredneatly to the skin surface (the surface of skin) even after lapse offive hours, whereas, with respect to the control substance, the cause ofthe makeup to come off takes place significantly by the sebum, where thepowder does not exist on the top of the wrinkle on the skin anddescending into the skin wrinkle grooves. Moreover, “shine” by the sebumis also seen.

Example 7

[0172] Under-makeup Emulsion

[0173] An under-makeup emulsion was prepared by the followingcomposition: parts by components weight oily squalane 4.0 phase cetyloctanoate 5.5 jojoba oil 1.5 cetanol 0.6 d-δ-tocopherol 0.02 glycerinemonooleate 0.2 glycerine 0.5 monostearate P.O.E. behenyl ether 1.6aqueous carboxy vinyl polymer 0.15 phase glycerine 17.0 methyl paraben0.3 xanthane gum 0.05 potassium hydroxide 0.09 inventive substance 5.0(Example 1) purified water 63.49

[0174] (Preparation Method)

[0175] The components of the oily phase were dissolved homogeneously at80° C. A mixture of aqueous phase components, in which the inventivesubstance (powder of Example 1) was dispersed homogeneously, was heatedto 80° C. and added to the homogeneously dissolved oily components andemulsified at 80° C. The mixture was cooled to 50° C. after storage forten minutes at 80° C., and an under-makeup emulsion was obtained.

[0176] (Evaluation of Usability)

[0177] (1) Samples

[0178] As a control substance (Comparative Example 2), an under-makeupemulsion, prepared in accordance with the Example 7 except substitutingthe purified water for the powder of the inventive substance (Example 1)among the aqueous phase components used in the composition of Example 7,was used.

[0179] (2) Method of Use

[0180] The under-makeup emulsion was evaluated based on comparison ofthe case of using the powder foundation prepared in Comparative Example1 with the under-makeup emulsion prepared in the present Example 7 andthe case of using the powder foundation prepared in Comparative Example1 with the control substance prepared in Comparative Example 2(under-makeup emulsion).

[0181] (3) Results of Evaluation

[0182] As for the method for evaluation, the five-stage evaluation wasalso performed in accordance with the aforementioned Example 5. Theresults were shown in Table 10. It may be seen from these results thatthe inventive substance has superior properties. TABLE 10 items ofComparative evaluation Example 7 Example 2 long wear 4.5 1.0transparency 4.0 2.1 extension on skin 3.6 3.2 makeup finish 4.3 2.5affixture 4.2 2.3 adhesion 4.0 3.0

Example 8

[0183] Preparation of Emulsified Foundation

[0184] An emulsified foundation was prepared in accordance with thefollowing composition; parts by components weight oily stearic acid 0.75phase glycerine 3.0 monostearate polyethylene glycol 0.5 monostearateP.O.E. sorbitan 1.5 monostearate glycerine tri-2-ethyl 3.0 hexanoatesorbitan sesquioleate 0.3 titanium dioxide 5.0 squalane 2.0 cetyloctanoate 8.2 talc 4.0 red iron oxide 0.3 yellow iron oxide 0.9 purpleiron oxide 0.3 aqueous polyethylene glycol 10.0 phase 200 carboxymethyl0.1 cellulose sodium xanthane gum 0.05 methyl paraben 0.3triethanolamine 0.7 magnesium aluminum 1.0 silicate inventive substance10.0 (Example 1) purified water 48.1

[0185] (Preparation Method)

[0186] Of the oily components, talc, titanium dioxide and organicpigments were homogeneously dispersed to give a mixture of the oilyphase, which was heated to 85° C. On the other hand, the mixture of theaqueous phase components, obtained on homogeneously dispersing theinventive substance and magnesium aluminum silicate in the aqueousphase, was heated to 85° C. as was the oily phase mixture. The aqueousphase then was added to the oily phase dispersion of 85° C. prepared asdescribed above and emulsified. After the end of the emulsification, theemulsion was held at 85° C. for 15 minutes and cooled up to 30° C. toproduce an emulsion type foundation.

[0187] (Evaluation of Usability)

[0188] (1) Samples

[0189] As a control substance (Comparative Example 3), an emulsifiedfoundation prepared in the same way as in Example 8 except substitutingthe purified water for the inventive substance in the aqueous phase inthe Example 8 was used.

[0190] (2) Method of Use

[0191] The control substance and the inventive substance were used bynine aesthetic persons in the panel alternately every other day for twoweeks. The evaluation was based on the results obtained.

[0192] (3) Results of Evaluation

[0193] The evaluation was also performed in five stages as in theExample 5 described above. Table 11 shows the results, from which it isseen that the inventive substance exhibits superior properties. TABLE 11items of Comparative evaluation Example 8 Example 3 long wear 4.6 1.2transparency 4.3 2.4 extension on skin 3.7 3.7 makeup finish 4.5 2.6affixture 4.4 2.5 adhesion 4.1 2.9

Example 9

[0194] Preparation of Body Deodorant

[0195] A body deodorant was prepared based on the following composition:Composition of the Body Deodorant components parts by No. componentsweight 1 talc treated with silicone 38.0 2 inventive substance 40.0(Example 1) 3 cyclic dimethyl 20.0 polysiloxane 4 cetyl octanoate 1.0 5glycerine tri-2-ethyl 1.0 hexanoate

[0196] (Preparation Method)

[0197] The components 1 and 2 were mixed in a Henschel mixer andpowdered by a pulverizer. The pulverized mass was transferred to aHenschel mixer and added to with a liquid mixture of the components 3 to5 as the oily components for mixing. The resultant mixture then waspowdered by a pulverizer to prepare a body deodorant.

[0198] (Evaluation)

[0199] A deodorant test then was conducted for evaluating the bodydeodorant produced.

[0200] (Deodorant Testing Method)

[0201] Eight healthy male persons in the panel who were recognized assuffering from strong foot smell were selected for member of a panel inthe evaluation and put to the test on the aforementioned body deodorant(inventive substance) admixed with the composite material prepared inExample 1. The state in which a person in the member wears a stockingand a shoe and is heated and stuffed for three hours is termed the“pre-using” state, and a functional test was conducted on the degree offoot smell at this time. The body deodorant was then coated on the footand the person in the panel then wears a stocking and a shoe and kept inthis state for 30 minutes to five hours. After this time interval, thedegree of foot smell was similarly evaluated. The test was carried outfor four days every day to find an average value.

[0202] (Standard for Evaluation)

[0203] The degree of foot smell was evaluated in seven stages of 0 to 6based on the following seven standards to find average values (scores)of the results of the eight persons in the panel.

[0204] 0: none

[0205] 1: very slight smell

[0206] 2: slight smell

[0207] 3: some noticeable smell

[0208] 4: noticeable smell

[0209] 5: strong smell

[0210] 6: very strong smell

[0211] The results are shown in the following Table 12: TABLE 12 timeelapsed (after coating of the inventive substance) scores 30 minutes 0 1hour 0 2 hours 0.4 3 hours 0.9 4 hours 2.0 5 hours 2.8 “before use”(control) 5.1

[0212] From the above test results, it may be seen that the bodydeodorant of the inventive substance (present invention) has a superiordeodorant effect.

[0213] Effect of Invention

[0214] The present invention provides a powder which specificallyadsorbs free fatty acids, in particular unsaturated fatty acids, adsorbsand solidifies the sebum secreted, forms a solid film so as not toobstruct skin physiology, has the same light reflection curve as thatfrom the skin surface and the skin feeling and which is superior in longwear effect for makeup and antibacterial effect, and which may beconveniently used for cosmetics. The present invention also provides acosmetics and a sebum-adsorbent having these superior effects by the useof these powders. Moreover, the powder in the present invention exhibitsthe operation of adsorbing, solidifying, or congealing the body odorcomponents and hence the present invention also provides a bodydeodorant employing the inventive powder.

[0215] It should be noted that other objects, features and aspects ofthe present invention will become apparent in the entire disclosure andthat modifications may be done without departing the gist and scope ofthe present invention as disclosed herein and claimed as appendedherewith.

[0216] Also it should be noted that any combination of the disclosedand/or claimed elements, matters and/or items might fall under themodifications aforementioned.

What is claimed is:
 1. A powder comprising a base substance usable as apowder for cosmetics, a hydroxyapatite and a zinc oxide.
 2. A powdercomprising a base substance usable as a powder for cosmetics, ahydroxyapatite coated on the surface of said substance and a zinc oxidefixed to the coating layer of said hydroxyapatite.
 3. The powder asdefined in claim 1 or 2, which is used for cosmetics.
 4. The powder asdefined in claim 1 or 2, which has an adsorbent property for sebumcomponents.
 5. The powder as defined in claim 1 or 2, wherein saidsubstance contains an inorganic powder and contains any one of a claymineral, a metal hydroxide, a metal oxide, a composite material thereof,and composite material(s) of one or more of these inorganic powders withan organic powder, wherein said clay mineral may be a syntheticmaterial.
 6. The powder as defined in claim 1 or 2, wherein said zincoxide contains at least one of low crystalline zinc oxide and amorphouszinc oxide.
 7. The powder as defined in claim 1, 2 or 6, wherein saidzinc oxide has a crystalline size of 1000 Å at the longest as obtainedfrom Scherrer's equation.
 8. The powder as defined in claim 1 or 2,wherein said substance contains a lamellar shape, a scale-like shape, aplate-like shape or a bar-like shape.
 9. The powder as defined in claim1 or 2, wherein the mean particle size of said substance is 0.1 to 600μm and the mean particle size of said zinc oxide is 0.01 to 1 μm. 10.The powder as defined in claim 1 or 2, containing 2 to 50 wt % ofhydroxyapatite and 2 to 8 wt % of zinc oxide based on the total weightof substance, hydroxyapatite and zinc oxide.
 11. A cosmetics comprisingthe powder as defined in any one of claims 1 to
 4. 12. The cosmetics asdefined in claim 11, containing 0.01 to 50 wt % of said powder.
 13. Asebum-adsorbent agent comprising the powder as defined in claim 1, 2 or4.
 14. A body deodorant comprising the powder as defined in claim 1, 2or 4.